EP3585836B1 - Suspension polyphasique de polymère et son utilisation - Google Patents

Suspension polyphasique de polymère et son utilisation Download PDF

Info

Publication number
EP3585836B1
EP3585836B1 EP18706827.5A EP18706827A EP3585836B1 EP 3585836 B1 EP3585836 B1 EP 3585836B1 EP 18706827 A EP18706827 A EP 18706827A EP 3585836 B1 EP3585836 B1 EP 3585836B1
Authority
EP
European Patent Office
Prior art keywords
water
suspension
multiphase
particulate
soluble polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP18706827.5A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP3585836A1 (fr
Inventor
Cédrick FAVERO
Alexandre OMONT
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SPCM SA
Original Assignee
SPCM SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SPCM SA filed Critical SPCM SA
Publication of EP3585836A1 publication Critical patent/EP3585836A1/fr
Application granted granted Critical
Publication of EP3585836B1 publication Critical patent/EP3585836B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5272—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using specific organic precipitants
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F2001/007—Processes including a sedimentation step
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/54—Aqueous solutions or dispersions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/14—Double emulsions, i.e. oil-in-water-in-oil emulsions or water-in-oil-in-water emulsions

Definitions

  • the present invention relates to a particulate multiphase suspension and its use in the technical fields of enhanced oil recovery in a deposit, hydraulic fracturing, treatment of mining effluents and drilling operations in civil engineering such as in oil operations. and gas.
  • the method most frequently implemented consists of injecting water into the deposit through injection wells dedicated to this purpose. This is called secondary recovery.
  • This second phase stops when the water/oil ratio is too high, that is to say when the quantity of water in the mixture produced by the producing wells is too high.
  • This secondary recovery thus makes it possible to obtain an additional recovery rate of the order of 10 to 20%.
  • Enhanced Oil Recovery RAP or EOR, acronym for "Enhanced Oil Recovery”
  • Their goal is to recover between 10 and 35% of additional oil compared to the initial quantity of oil.
  • enhanced oil recovery are known various thermal techniques, or not, such as the so-called electric, miscible, steam, or even chemical techniques for improved recovery of the oil remaining in place (see “Oil & gas science and technology” - TFP magazine, vol 63 (2008) n°1, pp 9-19 ).
  • oil is meant any type of oil, namely light oil as well as heavy oil, or even bituminous.
  • the present invention relates more specifically to enhanced oil recovery by chemical means involving the continuous injection of a fluid composition, otherwise called injection fluid, containing at least one water-soluble polymer, said composition being able to push the oil out of the rock.
  • a fluid composition otherwise called injection fluid
  • injection fluid containing at least one water-soluble polymer
  • petroleum is meant any type of oil, namely light oil as well as heavy oil, or even bituminous.
  • An oil generally results from the natural transformation of organic matter and is composed of a mixture of hydrocarbons.
  • petroleum and oil are used to designate the same material, with the exception of the mention of the composition of an emulsion.
  • the effectiveness of water injection sweeping is generally improved by the addition of water-soluble polymers.
  • the expected and proven benefits of the use of polymers, through the "viscosification" of the injected water, are the improvement of sweeping and the reduction of the viscosity contrast between the fluids to control their mobility ratio in the field, and this in order to recover the oil quickly and efficiently. These polymers increase the viscosity of water.
  • the injection fluid is in the form of a solution in which the viscosifying water-soluble polymer is completely dissolved.
  • water-soluble polymers powder, solution, emulsion.
  • the powder form is the most widely used.
  • the powder is dissolved in water or brine before being injected into the deposit. This essential step requires additional equipment and a long preparation time. Powder is traditionally preferred because of its cost, its stability, and when the project under consideration does not have major constraints of floor space, laden weight, or transfer of products over long distances.
  • the solution form contains the polymer dissolved in water. It is used very little because it cannot contain a large quantity of polymer because of the excessive viscosity provided by the polymer. Generally the maximum polymer concentration is about 2 to 5% by weight, but never exceeds 5%.
  • inverse emulsion water in oil
  • the polymer is in hydrophilic micrometric droplets emulsified with the help of surfactants in an oily continuous phase.
  • inverse emulsions contain between 20 and 60% by weight of polymer. They are particularly used in projects at sea, on offshore platforms because they do not require heavy equipment to, if necessary, invert the emulsions and prepare the injection fluid. They thus make it possible to limit the grip on the ground, the weight, and can be transferred by pumping over long distances.
  • WO 2009/047480 describes a fluid which may comprise seawater, a polymer of the hydroxyethylcellulose type, polypropylene glycol, NaCl salt and melamine (1,3,5-triazine-2,4,6-triamine). This fluid comprises 0.75% by weight, or less, of polymer of the hydroxyethylcellulose type.
  • compositions used in the field of hydraulic fracturing do not include more than 0.1% by weight of polymer and not more than 5% by weight of salt.
  • the document WO 2011/100665 describes a thickening composition and its use, for example in the field of oil recovery.
  • This composition does not include more than 3% by weight of water-soluble polymer and not more than 2% by weight of salt.
  • LDP Liquid Dispersion Polymer
  • the document WO2016069937 describes a polymeric composition comprising a polymer in powder form suspended in a solvent with an HLB greater than 8. This dispersion is anhydrous and preferably contains surfactants.
  • solvents in these compositions pose a safety problem during their transport, and during their handling to prepare the injection fluid.
  • the presence of these solvents and especially of surfactants can pose problems of compatibility with certain ingredients of the aqueous injection fluid, as well as problems of propagation in the underground formation.
  • the solvent and the surfactants can interact and form droplets which generate complex multiphase flows, as in the case of the use of inverse emulsions.
  • the oil industry is looking for enhanced oil recovery products and processes that are simpler using minimal equipment, safer using compatible products, less hazardous and easy to transfer from one storage location to another, all while minimizing the preparation time of the polymers, the surface area occupied, the total weight of the installations, and not causing propagation problems in the tank.
  • the Applicant has discovered that it is possible to formulate a polymer in powder form to form a liquid in the form of a particulate multiphase suspension, having a concentration by weight of polymer greater than 20%, without the problem of excessive viscosity, presenting good stability, and can be used without requiring specific solution treatment equipment.
  • multiphase suspension is meant a suspension containing at least two distinct phases, in this case, at least one aqueous phase and one solid phase.
  • the Brookfield viscosity is measured with a Brookfield model LVT apparatus, fitted with an LV module, the module being able to rotate at a speed of 30 revolutions per minute for example, the measurement being advantageously carried out at 20°C. This is of course the measurement of the viscosity of the multiphase suspension as defined according to the invention.
  • this viscosity is called Brookfield viscosity.
  • the density is measured at 25° C., at a pressure of 1 atm, that is to say 101,325 Pa.
  • the injection fluid contains fewer salts than the particulate multiphase suspension.
  • the particulate multiphase suspension contains substantially no solvent(s), and substantially no surfactant(s). Indeed, as explained above, their presence generates multiphase flows that are much more complex to control. Of course, when small amounts (less than 1% by weight) of solvent are present in the multiphase particulate suspension, this is not necessarily a problem. However, and preferably, the particulate multiphase suspension does not contain any solvent at all.
  • the particulate polyphasic suspension contains substantially no surfactant.
  • a presence of surfactant of less than 0.5% by weight, preferably less than 0.1% by weight, will not necessarily pose a problem.
  • the particulate polyphasic suspension contains no surfactant at all.
  • the particulate multiphase suspension comprises between 15 and 60% by weight of water-soluble polymer, preferentially between 20 and 45%, and more preferentially between 25 and 40%.
  • the water-soluble polymer is in the form of solid particles in the multiphase suspension. The water-soluble polymer is not dissolved in the multiphase suspension.
  • the suspensions contain between 300 and 750 kg of active polymer per m 3 of suspension, preferably from 400 to 750 kg/m 3 , more preferably from 500 to 750 kg/m 3 .
  • This provides a technical advantage in the processes in which the suspensions according to the invention are used, such as for example the lower occupation of the polymer storage volume.
  • the average size of the water-soluble polymer particles is between 10 ⁇ m and 400 ⁇ m, preferentially between 50 ⁇ m and 200 ⁇ m.
  • the water-soluble polymer particles can have a regular and spherical shape, like beads, or not regular.
  • the average size of the water-soluble polymer particles is the average size of the most important dimension, for example the diameter for spherical particles, measured with a laser measuring device using conventional techniques which are part of the knowledge of those skilled in the art. .
  • a device of the Mastersizer type from Malvern, for example the MS2000, can be used for this purpose.
  • This guy of apparatus makes it possible to measure, by laser diffraction, the particle size distribution of the particles in liquid medium or in solid form, preferably in the multiphase suspension.
  • the water-soluble polymer can be a natural polymer, such as for example xanthan gums, guar gums or other compounds of the polysaccharide family, or a synthetic or semi-synthetic polymer.
  • a synthetic polymer Preferably the water-soluble polymer is a synthetic polymer.
  • the water-soluble polymer is a synthetic polymer, it is preferably a polymer obtained from at least one nonionic monomer and/or at least one anionic monomer and/or at least one cationic monomer.
  • the nonionic monomer(s) that can be used in the context of the invention can be chosen, in particular, from the group comprising water-soluble vinyl monomers.
  • Preferred monomers belonging to this class are, for example, acrylamide, methacrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide and N-methylolacrylamide.
  • N-vinylformamide, N-vinyl acetamide, N-vinylpyridine and N-vinylpyrrolidone, acryloyl morpholine (ACMO) and diacetone acrylamide can be used.
  • a preferred nonionic monomer is acrylamide.
  • the anionic monomer(s) are preferably chosen from acrylic acid, methacrylic acid, itaconic acid, maleic acid, 2-acrylamido-2-methylpropanesulfonic acid (ATBS), vinylsulphonic acid, vinylphosphonic acid, said anionic monomer being non-salified, partially or totally salified, and the salts of 3-sulfopropyl methacrylate.
  • the cationic monomer or monomers that can be used within the scope of the invention can be chosen, in particular from monomers of the acrylamide, acrylic, vinyl, allylic or maleic type possessing a quaternary ammonium function. Mention may be made, in particular and without limitation, of quaternized dimethylaminoethyl acrylate (ADAME), quaternized dimethylaminoethyl methacrylate (MADAME), dimethyldiallylammonium chloride (DADMAC), acrylamido propyltrimethyl ammonium chloride (APTAC), and methacrylamido propyltrimethyl ammonium chloride (MAPTAC).
  • ADAME quaternized dimethylaminoethyl acrylate
  • MADAME quaternized dimethylaminoethyl methacrylate
  • DADMAC dimethyldiallylammonium chloride
  • ATAC acrylamido propyltrimethyl ammonium chloride
  • MATAC me
  • the water-soluble copolymer(s) may also include one or more hydrophobic monomers.
  • the documents WO2005100423 and WO201315003 exemplify suitable and advantageous hydrophobic monomers.
  • the water-soluble polymer is preferably an anionic polymer based on acrylamide, preferably a copolymer of acrylamide and acrylamide tert-butyl sulfonic acid (ATBS) optionally partially post-hydrolyzed, more preferably a terpolymer of acrylamide, acrylic acid and of acrylamido tert-butyl sulfonic acid (ATBS).
  • ATBS acrylamide tert-butyl sulfonic acid
  • the water-soluble polymer preferably contains between 10% and 50% molar of anionic monomer(s), more preferably between 25% and 40% molar.
  • the water-soluble polymer preferably contains between 1% and 10% molar ATBS.
  • the water-soluble polymer contains only anionic and nonionic monomeric units. In other words, it is preferably obtained from at least one type of anionic monomer and from at least one type of nonionic monomer.
  • the water-soluble polymer can also be structured by at least one structural agent, which can be chosen from the group comprising polyethylenically unsaturated monomers (having at least two unsaturated functions), such as for example the vinyl, allylic, acrylic and epoxy functions and mention may be made, for example, of methylene bis acrylamide (MBA), triallyamine, or also by macroinitiators such as polyperoxides, polyazoics and polytransfer agents such as polymercaptant polymers.
  • MBA methylene bis acrylamide
  • macroinitiators such as polyperoxides, polyazoics and polytransfer agents such as polymercaptant polymers.
  • the water-soluble polymer is not crosslinked. It can be linear or structured, i.e. branched, star (star-shaped), associative (containing hydrophobic groups), thermosensitive (with groups with an LCST), or comb (comb-shaped).
  • an LCST group corresponds to a group whose solubility in water for a given concentration is modified beyond a certain temperature and as a function of salinity.
  • This is a group exhibiting a transition temperature by heating defining its lack of affinity with the solvent medium.
  • the lack of affinity with the solvent results in an opacification or a loss of transparency which may be due to precipitation, aggregation, gelling or viscosification of the medium.
  • the minimum transition temperature is called "LCST” (lower critical solubility temperature, from the acronym “Lower Critical Solution Temperature”).
  • LCST lower critical solubility temperature
  • structured polymer is meant a non-linear polymer which has side chains so as to obtain, when this polymer is dissolved in water, a strong state of entanglement leading to very high low-gradient viscosities.
  • the polymers according to the invention have the primary functionality of viscosifying the water injected into the reservoirs containing oil to ensure mobility control without the need for crosslinking, that is to say inter-chain chemical bridging, being necessary. .
  • the viscosity is, for an identical structure and chemistry, all the higher as the size of the polymer chain is long. This is related to physical entanglements between the chains creating resistance to molecular mobility, which generates viscosity. In the context of the present invention, it is therefore advantageous to use polymers of high molecular weight.
  • high molecular weight is meant molecular weights of at least 1 million g/mol, preferably between 2 and 40 million g/mol, more preferably between 5 and 30 million g/mol.
  • the molecular weight is understood as weight average molecular weight.
  • the water-soluble polymers used do not require the development of a particular polymerization process. They can be obtained by all the polymerization techniques well known to those skilled in the art resulting in a polymer in powder form: gel polymerization followed by drying and grinding steps; precipitation polymerization; solution polymerization, followed by a spray drying step; reverse suspension polymerization to obtain microbeads; micellar polymerization whether or not followed by a precipitation step; post-hydrolysis or co-hydrolysis polymerization; so-called "template” polymerization, radical, or even controlled radical, and more particularly of RAFT type (Reversible Addition Fragmentation Chain Transfer).
  • RAFT type Reversible Addition Fragmentation Chain Transfer
  • the preferred method of production is the gel process followed by drying and grinding to obtain polymer particles of the desired average size.
  • the particulate multiphase suspension comprises between 20 and 40% by weight of at least one alkali metal salt and/or of at least one salt of an alkaline-earth metal.
  • the alkali metal salt and/or the alkaline earth metal salt is a salt of a halide.
  • the alkaline-earth metal salt is CaCl 2 or CaBr 2 , or a mixture of the two, and preferably a combination of the two. Even more preferentially, the ratio between CaCl 2 and CaBr 2 is between 10:1 and 1:2, preferentially between 8:1 and 2:1. These embodiments make it possible to obtain better performance.
  • the particulate multiphase suspension according to the invention also comprises at least one viscosifying agent different from the water-soluble polymer.
  • viscosifying agent different from the water-soluble polymer.
  • the Applicant has found that the performance was improved when the viscosifying agent was a cellulose derivative, and more preferably hydroxy cellulose and a derivative of hydroxy cellulose, and even more preferably hydroxyethyl cellulose.
  • the particulate multiphase suspension according to the invention preferably comprises between 0.01 and 5% by weight of viscosifying agent, more preferably between 0.1 and 1% by weight.
  • the particulate multiphase suspension according to the invention has a density of between 1.1 and 2, preferably between 1.3 and 1.9 kg/l.
  • the particulate multiphase suspension according to the invention comprises more than 10% by weight of water, preferably more than 15%, even more preferably more than 20%.
  • a person skilled in the art will be able to adjust the percentage by weight of each of the constituents of the particulate multiphase suspension so that the sum of the percentages is equal to 100.
  • the particulate multiphase suspension has a viscosity between 500 cps and 20,000 cps. Preferably, its viscosity is between 1000 and 8000 cps.
  • the multiphase particulate suspension according to the invention is prepared by first mixing water and the salt(s), then adding the viscosifying agent, and finally the particles of water-soluble polymer.
  • the preparation of the suspension is preferably carried out in such a way that before adding the water-soluble polymer particles, the density of the liquid in which the particles are added is between 1.1 and 2 kg/l, preferably between 1. 3 and 1.9 kg/l.
  • the injection fluid contains fewer salts (lower percentage by weight) than the particulate multiphase suspension.
  • One of the great advantages of the polymer suspension and of the method according to the invention is to be able to quickly and easily prepare an injection fluid with a concentrated form of water-soluble polymer.
  • the enhanced oil recovery process is simpler because it does not use heavy equipment to implement the form in which the polymer is delivered to the oil fields. It is faster and allows to minimize the preparation time of the polymer solutions, while not causing propagation problems in the tank. Finally, it consumes less space because the densities of the suspensions are high, and the suspensions contain between 300 and 750 kg of active polymer per m 3 of suspension, i.e. a large quantity of polymer per volume of product delivered (the suspension) .
  • the mixing of the suspension with the water or the brine is carried out for less than 1 hour, preferably for less than 10 minutes.
  • the injection fluid prepared from the mixture can be injected less than 1 hour, or even less than 15 minutes after the start of the mixture. between the multiphase suspension and water or brine. This short lead time is particularly advantageous for optimizing material flows in these often complex enhanced oil recovery operations.
  • the mixing between the multiphase suspension and the water or the brine is partly done in a static or dynamic mixer, or in an agitated tank, or in a device for dispersing the particulate polymer suspension.
  • the multiphase suspension is mixed with water or a brine containing less salts than the multiphase suspension to give an intermediate composition, said intermediate composition then being mixed with water or a brine containing less of salts than the multiphase suspension to give the injection fluid.
  • the multiphase suspension is added in line in a conduit carrying water or brine forming an injection fluid, said injection fluid being pumped directly into the reservoir, with no mixing step other than turbulence in the duct.
  • the injection fluid contains before its injection between 20 ppm and 5000 ppm by weight of one or more water-soluble copolymers as described above, preferably between 300 ppm and 4000 ppm.
  • the injection fluid at the time of its injection, has a viscosity of between 1 and 200 cps (centipoise), (viscosity measurements at 20° C. with a Brookfield viscometer with a UL module and at a speed of 6 revolutions per minute).
  • the injection fluid is then injected into an oil field, that is to say into a reservoir (or underground formation), according to any technique known to those skilled in the art in the methods also known as "RAP” or “EOR". Its preparation is carried out on site, just upstream of its injection into the deposit. In general, all the components introduced into the water or the brine to constitute the injection fluid are most often added to a circulation line of the aqueous solution or of the brine.
  • the suspension according to the invention can be used in all fields in which water-soluble polymers of high molecular weight are used, such as for example drilling operations, hydraulic fracturing and the treatment of mining effluents, but also water treatment. , papermaking and construction.
  • the suspension according to the invention is of particular interest in various fields such as drilling operations, hydraulic fracturing and the treatment of mining effluents. Indeed, one of the great advantages of the form of polymer according to the invention is that it can be prepared quickly and easily, and this with a concentrated form of easily transportable water-soluble polymer.
  • the present invention also relates to the use of the multiphase suspension according to the invention in a drilling operation. More specifically, the invention also relates to the use of the multiphase suspension according to the invention to prepare a composition of an aqueous drilling fluid, commonly called "drilling mud", used to drill an underground well, a tunnel, a trench or stake. It can be vertical drilling (VDD for Vertical Directional Driling) or horizontal (HDD for Horizontal Directional Drilling). The civil engineering and oil and gas recovery industries are particularly affected by these drillings.
  • VDD Vertical Directional Driling
  • HDD Horizontal Directional Drilling
  • the suspension according to the invention can be used alone as the main constituent of the drilling mud or as an additive in an existing drilling mud formulated with at least one other active ingredient such as: bentonite, sepiolite, attapulgite , surfactants, water or a polymer.
  • a rotary system is a correct form of drilling a pile, an oil or gas well. This system is based on the rotation of a string of drill rods to the base of which are attached a drill bit with multiple points, a bucket or a screw, in particular of the endless screw type. The drill bit, auger or bucket drills through the rock causing debris to accumulate as the drilling progresses.
  • a drilling fluid must be used, among other things, to bring this debris to the surface for disposal, so that the drill bit can continue to operate and the borehole can be kept clean. and free of debris at all times.
  • the drilling "mud” liquid must also ensure the stability of the borehole during the progress of the drilling but also during the stopping phases by ensuring the maintenance in suspension of the debris or "cuttings".
  • the drilling "mud” liquid must also make it possible to inhibit the swelling of the clays and thus avoid the blocking of the drill bit.
  • the suspension according to the invention makes it possible to adjust the viscosity of the excavation sludge and to manage the pressure in the excavation chamber with great precision.
  • Drilling devices other than the rotary device, such as the bucket, the hydro-cutter are sometimes used during drilling operations. Nevertheless, these devices still require the presence of a drilling fluid, or "drilling mud", to remove debris from the borehole or to otherwise perform functions related to drilling fluids.
  • the suspension according to the invention is particularly advantageous as an ingredient of a composition of an aqueous drilling liquid both in terms of the ease of implementation and in the application performance obtained.
  • the suspension according to the invention allows the use, with great ease of implementation, of high molecular weight polymers and the obtaining of a higher viscosity at an equivalent dosage.
  • the suspension according to the invention is particularly effective when the drilling operation is carried out in polluted soils, in particular by the presence of divalent cations, water with high salinity, cement pollution or any other contaminant providing an excess of electrolyte(s) responsible for the destruction of the viscosity by neutralization of the polymer.
  • the present invention also relates to the use of the multiphase suspension according to the invention in a hydraulic fracturing operation, in particular of oil and unconventional gas reservoirs.
  • the document WO2013/150203 describes this technology and a particularly advantageous polymeric composition.
  • Hydraulic fracturing has intended to create additional permeability and generate larger gas or oil production areas. Indeed, the low permeability, the natural barriers of compact layers, the waterproofing by the drilling operations strongly limit the production.
  • the gas or oil contained in the unconventional reservoir cannot easily migrate from the rock to the well without stimulation of the reservoir by hydraulic fracturing.
  • the suspension according to the invention is particularly advantageous both in terms of ease of implementation and in terms of the application performance obtained. Mention may be made of the improvement of the support properties, and the reduction of pressure drops.
  • the present invention also relates to the use of the multiphase suspension according to the invention in a mining effluent treatment operation.
  • the document WO2014/736624 describes this technology and a particularly advantageous polymeric composition.
  • the suspension according to the invention is particularly advantageous both in terms of ease of implementation and in terms of the application performance obtained. We can cite for example the improvement of the solid-liquid separation and the increase in the clarity of the extracted water.
  • the use of the multiphase suspension according to the invention has an advantage in a particular technique for treating mining effluents. This consists of combining a flocculant or a coagulant with a mining effluent, then discharging this treated effluent underwater.
  • a mining effluent is transported to a discharge zone consisting of an aquatic zone such as a pond or a lake.
  • the mining effluent is treated with a flocculant or a coagulant.
  • the effluent thus treated is discharged into the aquatic zone, near the water level or below the water level such that the treated effluent flows and falls into the aquatic zone in which the solid part sediments at the bottom, and the aqueous part ends up in the water of the aquatic zone.
  • the effluent is transported in a pipe, the outlet of the pipe through which the treated effluent leaves is positioned close to the aquatic zone, or is immersed in the aquatic zone.
  • the treated effluent exits directly into the aquatic zone, below the water level.
  • the depth of immersion of the pipe is preferably from 0.1 to 10 meters.
  • the use of the multiphase suspension according to the invention in this process allows the effective treatment of mining effluent. Compaction during sedimentation is improved and so is water quality.
  • the figure 1 represents a graph showing the evolution of the pressure drop as a function of the quantity of injection fluid measured in volume equivalent to the pore volume, and this for an injection fluid A containing 2000 ppm of water-soluble polymer, and prepared at from a suspension of particles of acrylamide terpolymer, of acrylic acid and of ATBS with a molecular weight of 12 million g/mol, suspended in an oil.
  • the picture 2 represents a graph showing the evolution of the pressure drop as a function of the quantity of injection fluid measured in volume equivalent to the pore volume, and this for an injection fluid B containing 2000 ppm of water-soluble polymer and prepared from of a particulate multiphase suspension according to the invention and in which the water-soluble polymer is a terpolymer of acrylamide, acrylic acid and ATBS with a molecular weight of 12 million g/mol.
  • Injecting polymer into a porous medium is a good way to ensure proper propagation of molecules within the reservoir with minimal damage. Injectivity is evaluated by measuring pressure drops continuously recorded via pressure sensors placed on either side of the system.
  • the injection of the injection fluids was carried out with water-saturated Bentheimer type rocks.
  • the average particle size of the water-soluble polymer is 160 ⁇ m.
  • an injection fluid A is prepared from a mixture of particles of acrylamide terpolymer, acrylic acid and ATBS with a molecular weight of 12 million g/mol, suspended in an oil added with bentonite, said suspension comprising 30% by weight of polymer and 66% of solvent organic (Exxsol D100), and 4% by weight of bentonite.
  • injection profile of injection fluid A shows a constant increase in pressure drop. This increase demonstrates the poor propagation of the injection fluid A which progressively clogs the rock. Applied in an oil field, it can cause irreversible damage and lead to a total loss of injectivity.
  • an injection fluid B is prepared from a particulate multiphase suspension according to the invention of particles of acrylamide terpolymer, acrylic acid and ATBS with a molecular weight of 12 million. g/mol, said suspension comprising (by weight): 36% terpolymer, 25% CaCl 2 , 18% CaBr 2 , and 0.05% hydroxyethyl cellulose.
  • injection profile of injection fluid B shows a stabilization of the pressure drop after the injection of a volume of fluid equivalent to 3 pore volumes. The pressure drop then remains stable during the injection, demonstrating very good propagation of the injection fluid B.
  • the multiphase suspension according to the invention has the advantage of being stable for more than 6 months. It does not contain any solvent or surfactant that could be harmful during injection. It is prepared quickly and without the need for a complex dissolving apparatus.
  • this particulate multiphase suspension in an enhanced oil recovery process makes it possible to simplify the step of preparing the injection fluid and makes it possible to obtain excellent results in terms of injectivity.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Water Supply & Treatment (AREA)
  • Hydrology & Water Resources (AREA)
  • Mining & Mineral Resources (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Fluid Mechanics (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Removal Of Floating Material (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Colloid Chemistry (AREA)
EP18706827.5A 2017-02-24 2018-02-15 Suspension polyphasique de polymère et son utilisation Active EP3585836B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1751501A FR3063292B1 (fr) 2017-02-24 2017-02-24 Suspension polyphasique de polymere et son utilisation
PCT/FR2018/050361 WO2018154219A1 (fr) 2017-02-24 2018-02-15 Suspension polyphasique de polymère et son utilisation

Publications (2)

Publication Number Publication Date
EP3585836A1 EP3585836A1 (fr) 2020-01-01
EP3585836B1 true EP3585836B1 (fr) 2022-04-06

Family

ID=59070780

Family Applications (1)

Application Number Title Priority Date Filing Date
EP18706827.5A Active EP3585836B1 (fr) 2017-02-24 2018-02-15 Suspension polyphasique de polymère et son utilisation

Country Status (7)

Country Link
US (1) US11118101B2 (pt)
EP (1) EP3585836B1 (pt)
CN (1) CN110168012B (pt)
BR (1) BR112019013997B1 (pt)
CA (1) CA3048808C (pt)
FR (1) FR3063292B1 (pt)
WO (1) WO2018154219A1 (pt)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11566172B2 (en) * 2017-12-20 2023-01-31 Halliburton Energy Services, Inc. Downhole high temperature rheology control
FR3100814B1 (fr) 2019-09-17 2021-11-05 S N F Sa Dispersion aqueuse de polymere hydrosoluble ou hydrogonflable
FR3117498B1 (fr) 2020-12-16 2023-11-10 Snf Sa Suspension polyphasique de polymère hydrosoluble

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5684075A (en) * 1995-02-21 1997-11-04 Phillips Petroleum Company Compositions comprising an acrylamide-containing polymer and process therewith
FR2868783B1 (fr) 2004-04-07 2006-06-16 Snf Sas Soc Par Actions Simpli Nouveaux polymeres amphoteres associatifs de haut poids moleculaire et leurs applications
WO2005103091A1 (en) 2004-04-21 2005-11-03 Ciba Specialty Chemicals Water Treatments Limited Composition and method of preparing high solid emulsions
EP2075300A1 (en) * 2007-10-09 2009-07-01 Bp Exploration Operating Company Limited Wellbore fluid
FR2945542B1 (fr) 2009-05-18 2013-01-11 Snf Sas Nouvelles formulations de polymeres hydrosolubles et additifs stabilisants permettant l'injection d'un compose unique utilisables dans les fluides d'injections pour la recuperation assistee chimique du petrole
EP2348089A1 (en) * 2010-01-26 2011-07-27 S.P.C.M. Sa Water-soluble polymers for oil recovery
CA2791853C (en) * 2010-02-12 2018-03-06 Rhodia Operations Rheology modifier compositions and methods of use
US9611416B2 (en) * 2010-10-25 2017-04-04 Isp Investments Llc Salt-tolerant, thermally-stable rheology modifiers
EP2617347B1 (en) 2011-07-28 2014-12-31 Olympus Medical Systems Corp. Endoscope
FR2988730B1 (fr) 2012-04-03 2015-01-16 Snf Sas Nouvelle composition aqueuse de fluide de fracturation et procede de fracturation mettant en oeuvre le fluide
FR2994706B1 (fr) * 2012-08-27 2014-08-22 Spcm Sa Centre de preparation d'additifs pour des operations de fracturation hydraulique et procede de fracturation hydraulique mettant en oeuvre le centre de preparation
RU2644773C9 (ru) 2012-11-14 2019-04-18 Басф Се Способ добычи нефти третичными методами
FR3004458A1 (fr) * 2013-04-11 2014-10-17 Rhodia Operations Fluides de fracturation a base de polymeres associatifs et de tensioactifs labiles
US10696890B2 (en) * 2014-09-30 2020-06-30 Nippon Shokubai Co., Ltd. Methods of liquefying and shrinking water-absorbable resins in a water-containing state
WO2016069937A1 (en) 2014-10-31 2016-05-06 Chevron U.S.A. Inc. Polymer compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
BR112019013997A2 (pt) 2020-02-11
CN110168012B (zh) 2022-08-12
FR3063292B1 (fr) 2020-01-31
BR112019013997B1 (pt) 2022-12-20
CN110168012A (zh) 2019-08-23
FR3063292A1 (fr) 2018-08-31
CA3048808A1 (en) 2018-08-30
CA3048808C (en) 2023-05-02
US11118101B2 (en) 2021-09-14
EP3585836A1 (fr) 2020-01-01
US20190330517A1 (en) 2019-10-31
WO2018154219A1 (fr) 2018-08-30

Similar Documents

Publication Publication Date Title
You et al. Experimental study on spontaneous imbibition of recycled fracturing flow-back fluid to enhance oil recovery in low permeability sandstone reservoirs
EP3601222B1 (fr) Fluide de fracturation comprenant un (co)polymere d'une forme cristalline hydratee de l'acide 2-acrylamido-2-methylpropane sulfonique et procede de fracturation hydraulique
CA2698226C (fr) Fluide de forage contenant des nanotubes de carbone
EP3585836B1 (fr) Suspension polyphasique de polymère et son utilisation
US7549472B2 (en) Method for increasing the production of hydrocarbon liquids and gases
WO1996023849A1 (en) Polymeric earth support fluid compositions and method for their use
EP3947558A1 (fr) Emulsion inverse pour la fracturation hydraulique
EA028131B1 (ru) Целлюлозные нановискеры для обслуживания скважин
Ahmadi et al. Colloidal gas aphron drilling fluid properties generated by natural surfactants: experimental investigation
FR2986797A1 (fr) Nouvel agent inhibiteur de gonflement des argiles, compositions comprenant ledit agent et procedes mettant en oeuvre ledit agent.
FR3075219B1 (fr) Composition comprenant un (co)polymere hydrosoluble encapsule dans une enveloppe et son utilisation dans la recuperation assistee du petrole et du gaz
WO2020094961A1 (fr) Procede de recuperation assistee de petrole par injection d'une composition aqueuse polymerique
WO2020169478A1 (fr) Formulations moussantes pour la recuperation assistee du petrole
Aghdam et al. Studying the effect of various surfactants on the possibility and intensity of fine migration during low-salinity water flooding in clay-rich sandstones
EP3571261B1 (fr) Procede de recuperation assistee de petrole par injection d'une composition aqueuse polymerique contenant des microgels
JPS5968495A (ja) 掘削用流体及び掘削装置から汚染物質を除去する方法
WO2021239599A1 (fr) Procédé de récupération assistée de pétrole dans une formation souterraine carbonatée
FR3122656A1 (fr) Polymere amphotérique associatif hydrosoluble comme modificateur de rheologie pour traitement souterrain
WO2016110655A1 (fr) Additif pour injectivité
Peter et al. A Comparative Study of Locally designed and Imported Alkaline-Surfactant-Polymer Flooding for Enhanced Oil Recovery
SONY et al. Recovery of Crude Oil by Chemical Flooding Method Using SDS and Gum Arabic Mixtures.
CA2728489A1 (fr) Methode de recuperation assistee d'hydrocarbures utilisant des polymeres associatifs
WO2016110654A1 (fr) Additif pour injectivité
BE671288A (pt)

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20190709

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20201204

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20211109

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

RAP3 Party data changed (applicant data changed or rights of an application transferred)

Owner name: SPCM SA

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1481318

Country of ref document: AT

Kind code of ref document: T

Effective date: 20220415

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: FRENCH

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602018033319

Country of ref document: DE

REG Reference to a national code

Ref country code: NO

Ref legal event code: T2

Effective date: 20220406

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20220406

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1481318

Country of ref document: AT

Kind code of ref document: T

Effective date: 20220406

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220406

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220406

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220808

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220406

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220406

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220707

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220406

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220406

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220706

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220406

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220406

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220406

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220406

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220806

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602018033319

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220406

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220406

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220406

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220406

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220406

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220406

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20230110

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220406

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220406

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230527

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220406

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20230228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230215

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230228

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230228

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20220406

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230215

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20230228

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20240213

Year of fee payment: 7

Ref country code: GB

Payment date: 20240221

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NO

Payment date: 20240123

Year of fee payment: 7

Ref country code: FR

Payment date: 20240227

Year of fee payment: 7